|Publication number||US7951316 B2|
|Application number||US 11/099,944|
|Publication date||May 31, 2011|
|Filing date||Apr 5, 2005|
|Priority date||Apr 5, 2005|
|Also published as||US20060220272|
|Publication number||099944, 11099944, US 7951316 B2, US 7951316B2, US-B2-7951316, US7951316 B2, US7951316B2|
|Inventors||Jeffrey M. Smith, Duane E. Peterson, Harold H. Seymour|
|Original Assignee||Exxonmobil Chemical Patents Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (51), Non-Patent Citations (2), Referenced by (1), Classifications (33), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The invention generally relates to a process for forming an annular member comprising one or more thermoplastics. The annular member thus formed is particularly useful in pipe seal applications.
In applications such as pipe seals, the governing specifications require the material to have a low compression set. Thermoset rubbers (TSR), those vulcanized or cross-linked after molding, have typically been used. Thermoplastics and thermoplastic elastomers have been proposed to replace TSR in many applications, particularly dynamically vulcanized thermoplastic elastomers, e.g., thermoplastic vulcanizates (TPV). A TPV typically consists of a vulcanized rubber particle phase dispersed within a continuous thermoplastic phase. Those currently proposed to meet typical pipe seal specifications are grades having a hardness of approximately 45-65 Shore A. To form a ring member from an extruded profile, there must necessarily be a joint or weld. The softer grades of TPVs do not always heat weld in a welding process with adequate strength as compared to a vulcanized splice in a TSR. This is often due in soft TPVs to the higher content of dispersed rubber phase and decreased content of hard thermoplastic. In addition, the joint or weld, can provide a leak path both during pressure and vacuum testing of the piping system and its subsequent use if the weld joint is not effective.
Seals for small pipe diameters (e.g., 12 inch diameter) can be prepared by injection molding which avoids a need for a weld. However, seals having large diameters (e.g., greater than 12 inch diameter) or with lower unit volume are not typically suitable for injection molding processes due to high tooling and equipment costs. Instead, extruded seal material profiles are cut to length, formed into a ring, and then welded or joined through a thermal welding process or vulcanized splicing. Thus there exists a need in the art for an improved process to provide larger diameter pipe seals that can be fabricated from thermoplastic materials.
In the thermal welding process excess thermoplastic extends upon joining of the ends thus causing leaking or substandard seal performance. Thus, the heat-welded joint of thermoplastic, particularly thermoplastic elastomer, has substandard performance with respect to the thermoset rubber seals that utilize a vulcanized splice with little excess. Thus TPE seals have been inadequate for more demanding applications such as sewer pipes due to weld quality and long-term performance. The present invention is directed to overcoming these and other problems.
In accordance with an exemplary form of the present invention there is provided a process comprising extruding a strip of molten thermoplastic material through an extrusion die wherein the strip has a generally continuous cross-sectional profile and a leading end and a trailing end. Subsequent to extruding the strip and without substantially cooling the strip, the leading end and the trailing end are joined to form a joint there between by compression molding of the leading and trailing ends at a temperature sufficiently high to allow plastic flow in the area of the joint. The extrusion process imparts a predetermined cross-sectional profile to the extrudate. During the compression molding, the mold imparts the predetermined cross-sectional profile to the joint section.
In exemplary embodiments, the thermoplastic material may comprise one or more of engineering thermoplastics, thermoplastic elastomers (TPE), and mixtures thereof. Particular suitable thermoplastic materials will include dynamically vulcanized TPE, or thermoplastic vulcanizate (TPV). Particularly suitable are the polyolefin TPV compounds comprising at least one non-crosslinked polyolefin thermoplastic phase and at least one cross-linked polyolefin rubber phase. Other suitable thermoplastics include the thermoplastic polyolefins (TPO) without a cross-linked phase, such as homopolymers of ethylene or propylene, or copolymers with each together, and copolymers of ethylene or propylene, or together, with other polymerizable C4-C8 comonomers; styrene block copolymers (SBC) and blends of such copolymers, both those considered thermoplastic and those exhibiting the properties of thermoplastic elastomers; and blends of polyolefins, or blends of one or more of them, with SBC copolymers. Thermoplastic polyurethane elastomers will also be suitable, alone or in blends.
An exemplary process comprises extruding the thermoplastic material (or even one or more coextruded thermoplastics, optionally with the TPE) at an elevated temperature onto a movable fixture; interrupting the extruding of the material; moving the fixture so as to bring the leading end of the extrudate to a predetermined relationship to the trailing end; and, before said trailing end cools to a predetermined cooled temperature, engaging the leading end and the trailing end in a mold under pressure to form a joint section in order to form an annular member of the thermoplastic material. In this exemplary process a shaped extrusion die imparts a predetermined profile to the extrudate and the mold imparts the predetermined profile in the joint section. The annular member thus formed may be adapted to provide a generally fluid tight seal between adjacent fluid carrying conduits. The use of a coextruded outer thermoplastic plus an inner thermoplastic elastomer provides for a stiffer profile, more dimensionally stable shape, even at higher use temperatures, while retaining the sealing capabilities of the thermoplastic elastomer.
In some embodiments the movable fixture may include a rotating planar surface onto which the extrudate is positioned. The planar surface may be rotated to bring the leading end of the extrudate into engaged relationship with the trailing end. Alternately, the movable fixture may include a rotatable molding cylinder having an outer deposit-receiving surface. The extrudate can be directed onto the surface as the molding cylinder rotates so that the leading end of the extrudate may be brought into engaged relationship with the trailing end.
An exemplary apparatus includes an extruder having an exit die for forming a polymer extrudate having a leading end, an implement for severing later extruded polymer extrudate to create a trailing end, a rotatable fixture having a deposit-receiving surface for receiving the polymer extrudate and a compression molding mechanism. The rotatable fixture is operable to return the leading end of extrudate to a position in contact with the trailing end. The compression molding mechanism is adapted to cooperate with the rotatable fixture to form a joint in the polymer extrudate at a position where the leading end and trailing end are in contact.
By using a thermoplastic extruder, and specialized downstream equipment, continuous seals can be produced with superior spliced joints, automatically, and in-line with the extrusion process.
One advantage of exemplary forms of the present invention is that enhanced performance TPVs can replace TSRs to form large diameter pipe seals.
Another advantage of exemplary embodiments is that the splicing operation is completed without the time or energy expenditures required in vulcanization of TSRs.
Another advantage of exemplary embodiments is that the quality of the spliced joint is improved as compared to heat welding because the operation is performed on the molten TPV prior to significant cooling. The joints may exhibit superior strength and minimal flashing as compared to standard hot plate welding on TPVs.
Another advantage of exemplary embodiments is the reduced tooling and equipment costs as compared to an injection molding process. For example, one extrusion die may be capable of producing seals for several sizes of pipe.
Still other advantages of exemplary embodiments of the present invention will be apparent to those having skill in the art upon a reading and understanding of the specification.
Thermoplastic Elastomer (TPE): a diverse family of rubber like materials that, unlike conventional vulcanized rubbers, can be processed and recycled like thermoplastic materials. Typical examples include blends of “hard” crystalline, semi-crystalline, or glassy polymers (for instance those having a Tm greater than about 110° C. or Tg greater than about 60° C., as measured by differential scanning calorimetry (DSC), more preferably with amorphous or low-crystallinity polymers (Tm less than about 90° C. or Tg less than 60° C. by DSC). Examples of hard polymers include the non-polar and polar engineering resins such as polypropylene, polyethylene, polyamide, polycarbonate, and polyester resins. The “soft” polymers include most rubbers, particularly the non-polar olefin rubbers, for hard polyolefins, and polar rubbers for polar hard resins. Non-polar rubbers include ethylene-propylene rubber, very low density polyethylene copolymers comprising C4 to C8 α-olefin or vinyl aromatic comonomers, butyl rubber, natural rubber, styrene-butadiene rubber butadiene rubber, butadiene rubber and the like. Compatibilizing block copolymers and/or functionalized polymers are often used to improve overall engineering properties where incompatibility may exist as in blends of apolar and polar polymers.
Thermoplastic Vulcanizate (TPV): a thermoplastic elastomer with a chemically crosslinked rubbery phase, produced by dynamic vulcanization; TPVs provide functional performance and properties similar to conventional thermoset rubber products, but can be processed with the speed, efficiency and economy of thermoplastics; in addition to simpler processing, principal advantages of TPVs compared to thermoset rubber products include easier recycling of scrap and closer, more economical control of dimensions and product quality.
Dynamic Vulcanization: the process of intimate melt mixing a thermoplastic polymer and a suitable vulcanizable rubbery polymer with a cross-linking or vulcanization agent to generate a thermoplastic elastomer with a chemically crosslinked rubbery phase, resulting in properties closer to those of a thermoset rubber when compared to the same uncrosslinked composition. Thermoplastic vulcanizates and processes for preparing them are well known in the art, see for example, U.S. Pat. Nos., 4,130,535, 4,311,628, 4,594,390, and 5,672,660, and “Dynamically Vulcanized Thermoplastic Elastomers”, S. Abdou-Sabet, et al, Rubber Chemistry and Technology, Vol. 69, No. 3, Jul.-Aug. 1996, and references cited therein.
Styrene Block Copolymers: the SBC thermoplastics and thermoplastic elastomers useful in the invention are block copolymers of styrene/conjugated diene/styrene, with the conjugated diene optionally being fully or partially hydrogenated, or mixtures thereof. Generally this block copolymer may contain 10 to 50 weight %, more preferably 25 to 35 weight %, of styrene and 90 to 50 weight %, more preferably 75 to 35 weight % of the conjugated diene, based on said block copolymer. Most preferred, however, is a block copolymer which contains 28 to 35 weight % of styrene and 68 to 72 weight % of the conjugated diene. The conjugated diene is selected from butadiene, isoprene or mixtures thereof. Block copolymers of the styrene/conjugated diene/styrene type are SBS, SIS, SIBS, SEBS and SEPS, and SEEPS block copolymers.
These block copolymers useful are known in the art, and are further described in Canadian Pat. No. 2,193,264 and in International Pat. Applications WO 96/20248; WO 96/23823; WO 98/12240; and WO 99/46330. They are generally prepared by butyl lithium initiated sequential anionic polymerization, but coupling of living S-B/S diblocks or bifunctional initiation are also known methods. See, in general, Thermoplastic Elastomers (2nd Ed.), Ch. 3, G. Holden, N. Legge, et al (Hanser Publishers, 1996).
Thermoplastic Polyurethane: another suitable thermoplastic is thermoplastic polyurethane (TPU) prepared from substantially difunctional ingredients, i.e. organic diisocyanates and components being substantially difunctional in active hydrogen containing groups, particularly those that have at least one major Tg of less than 60° C. However, often minor proportions of ingredients with functionalities higher than two may be employed. This is particularly true when using extenders such as glycerol, trimethylol propane, and the like. Any of the TPU materials known in the art within this description can be employed within the scope of the present invention. The preferred TPU is a polymer prepared from a mixture comprising at least one organic diisocyanate, at least one polymeric diol and at least one difunctional extender. The TPU can be prepared by prepolymer, quasi-prepolymer or one-shot methods commonly used in the art, see International Pat. Application No. WO 01 10950 (A1) (above) and references cited therein. Thermoplastic vulcanizates comprising TPU, both high and low Tg TPU's are also suitable.
In this exemplary embodiment, molten material flows through an extrusion head 22 and is positioned onto a movable fixture 26 having a rotatable turntable 30. Turntable 30 includes a generally planar deposit-receiving surface 34. In this exemplary embodiment, the positioning and rotational speed of the turntable 30 is controlled relative to the flow from the extrusion head 22 to provide a continuous extrudate having a leading end 36. In this exemplary embodiment, apparatus 10 further includes an implement such as knife (not shown) for interrupting the flow from the extrusion head 22 to create a trailing end 39 of extrudate 18.
The extrusion process imparts a predetermined cross-sectional profile to extrudate 18. In this exemplary embodiment, the molten extrudate 18 is able to generally retain a predetermined three-dimensional shape during the extrusion process while turntable 30 is rotated.
As best seen in
With reference again to
In this exemplary embodiment, when sufficient volume of extrudate 18 is deposited onto surface 34 so that trailing end 39 meets leading end 36, turntable 30 is repositioned to place molding region 55 at the compression molding station 40 by rotating turntable 30 a predetermined indexed arc α.
The ring member thus formed is allowed to cool to a predetermined temperature and is then removed from the turntable 30. The turntable 30 is then recycled back to a predetermined position at the extrusion station 10. In this exemplary process, repositioning turntable 30 is accomplished by another rotation step.
In a second exemplary embodiment, positioning the turntable 30 at a compression molding station 40 comprises a physical transfer of the turntable 30. In this exemplary process, another turntable 30 may be positioned under the extrusion head 22 to receive a fresh extrudate stream while the first extrudate stream undergoes the compression molding step. The use of more than one turntable 30 may be preferable to obtain a more efficient production system.
For ease of processing, the flow of extrudate may be only momentarily interrupted in order to create trailing end 39 and position turntable 30 at the compression molding station. Thus, in another exemplary embodiment, illustrated in
In this exemplary embodiment, melt diverting system 62 includes a conveyor 66 for directing the flow of extrudate 18. The melt diverting system includes an implement such as knife 38′ for momentary interruption of the flow of material in order to create a trailing end 39 of extrudate 18. After a brief interruption, the flow of material is resumed. Because there may be a time lag until a turntable 30 is properly positioned to receive the extrudate, excess material is diverted to a collection site 70. In the exemplary embodiment, the conveyor 66 is movable such that excess material carried thereon may be diverted away from turntable 30 to collection site 70. In the exemplary embodiment, the chosen material may be readily recycled from the collection site 70.
Knife 72 and conveyer 66 operate in coordinated movement with extruder 12 and turntable 30 to deliver a predetermined amount of material to surface 34. After the predetermined volume of material has been delivered, the molding region 55 of turntable 30 is positioned at compression molding station 40 while the flow of material is diverted. When a turntable 30 is again positioned at the extrusion station 11, the flow of material is interrupted again, in order to create a leading end of fresh extrudate to be deposited onto surface 34. Conveyor 66 is re-positioned in order to deliver extrudate to surface 34, and the process is repeated. Additional fixturing (not shown) may be employed to accurately guide the extrudate 18 into a desired position. The nature of the exemplary thermoplastic elastomeric material allows for the collection and in-line recycling of the scrap or flash created during the exemplary processes. Thus, the overall scrap rate can be minimized.
Various configurations of a molding station may be utilized. For example,
In another exemplary embodiment, illustrated in
A rotatable molding cylinder 180 includes a deposit-receiving outer surface 182 operable to receive and support molten extrudate 168. The outer surface 182 may include one or more locating and shaping grooves 184. Molding cylinder 180 may further include vacuum holes 185 formed in groove 184 for enhanced retention of the extrudate on the rotating cylinder.
In this exemplary embodiment, the molding cylinder 180 is further adapted for reciprocal movement along its longitudinal axis 186. In this embodiment, a first compression molding station 156 is spaced from the extrusion station 154 such that reciprocal movement of the molding cylinder 180 is operable to move the extrudate 168 from the extrusion station 154 to the compression molding station 156 without removal of the extrudate 168 from the deposit-receiving outer surface 182. In this exemplary embodiment, cylinder 180 may receive a plurality of extrudate streams to be compression molded. Thus, reciprocal movement of cylinder 180 must be sufficient to allow each extrudate stream to be positioned at the first compression molding station 156. Alternately, additional compression molding stations may be utilized to accommodate a plurality of extrudate streams.
The first compression molding station 156 includes a mold section 188 movable toward and away from molding cylinder 180 in a radial direction via operation of a linear movement apparatus in a manner similar to that described in previous embodiments. Mold section 188 includes a molding cavity 189 adapted to mate with the formed extrudate 168, although the cavity 189 may be slightly undersized, from 5% to 10%, for adequate compression of the extrudate 168 into the mold section 188.
An alternate embodiment of a compression molding station 156′ is illustrated in
The nature of the thermoplastic elastomeric material allows for this type of automated production. The molten thermoplastic elastomer, unlike most thermoplastics, retains its shaped profile during the extrusion process. In the compression molding process, the molten extrudate can be readily molded to form the joint, without the need for a vulcanization step as necessary for thermoset material. Additionally, the formed ring member does not have to cool for an extended period of time before it can be removed from the molding cylinder.
An alternate embodiment of a rotatable molding cylinder 180 replaces this fixture with the fluid carrying conduit or pipe. In this embodiment the conduit is rotated under the extruder exit die along a longitudinal axis so that the leading end engages the pipe in the final installed location, typically on the spigot end, and the subsequent extrudate is wrapped around the conduit until the trailing end is severed and positioned in proximity to the leading end. A shaping roller may be utilized to further improve thermal adhesion between the extrudate and the conduit surface. The leading and trailing ends of the extrudate are then compression molded or roll formed as described in previous embodiments. The seal is then allowed to cool in place, where the natural shrinkage improves seal to conduit adhesion and provides an additional interference fit.
In yet another exemplary embodiment a second thermoplastic material may be utilized to improve adhesion between the extrudate and the conduit. This process includes an apparatus adapted for co-extrusion. A first extruder applies a first material to exit die 22 while a second extruder applies a second material to the same extrusion die. The extrusion die is adapted with specially designed flow channels that allow both materials to exit the die in a laminar flow so that the extrudate appears as a single part with two distinctive materials of similar or varied physical properties and/or chemical properties in different cross-sectional areas. This embodiment comprising multiple materials (2 or more) formed into an annular member, joined at the ends, and cooled may be practiced with each of the embodiments described.
Typical designs for gaskets that are currently used in this field are described in the following U.S. Pat. Nos.; 6,336,640, and 6,550,775B2. These patents reference gasket having one or more materials as previously described
In the described exemplary embodiments, the compression-molding process occurs while the extrudate is still in a molten state. In an exemplary process, the extrudate temperature should be in excess of 375° F. (190° C.), for typical polyolefin-based TPV materials, to prevent visible flow lines. It has been discovered that the temperature of the mold section affects the finished quality of the joint section. Thus, using anodized aluminum tooling, the mold section should be utilized at a temperature less than about 250° F. (120° C.) to prevent sticking and deformation of the extrudate. Sufficient pressure should be added to the mold section to minimize a parting line. Successful trials were accomplished using a minimum of 1500 PSI (10.3 mPa) on the projected area of the splice. The mold section can be moved away from the formed ring member after sufficient cooling. It has been found that cooling to 180° F. (80° C.) provides ample cooling.
Thus the exemplary apparatus and processes for forming an annular pipe seal achieve the above stated objectives.
Having described the features, discoveries and principles of the invention, the manner in which it is constructed and operated, and the advantages and useful results attained; the new and useful structures, devices, elements, arrangements, parts, combinations, systems, equipment, operations, methods and relationships are set forth in the appended claims.
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|U.S. Classification||264/210.1, 264/210.3, 264/210.2, 264/209.3, 264/212, 264/152, 264/148, 264/149|
|Cooperative Classification||B29C66/71, B29C66/8322, B29C47/0014, B29C47/0866, B29C47/0038, B29C66/1122, B29C47/004, B29C47/0035, B29C53/50, B29C66/4324, B29L2031/7096, B29C2791/001, B29L2031/265, B29D99/0085, B29C66/49, B29C66/4322, B29C65/028, B29C65/7847|
|European Classification||B29D99/00Q2, B29C65/02T10, B29C66/43, B29C66/1122, B29C47/00L, B29C47/08R|
|Jun 3, 2005||AS||Assignment|
Owner name: ADVANCED ELASTOMER SYSTEMS, L.P., OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SMITH, JEFFREY M.;PETERSON, DUANE E.;SEYMOUR, HAROLD H.;REEL/FRAME:016300/0909;SIGNING DATES FROM 20050513 TO 20050601
Owner name: ADVANCED ELASTOMER SYSTEMS, L.P., OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SMITH, JEFFREY M.;PETERSON, DUANE E.;SEYMOUR, HAROLD H.;SIGNING DATES FROM 20050513 TO 20050601;REEL/FRAME:016300/0909
|Jun 24, 2009||AS||Assignment|
Owner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ADVANCED ELASTOMER SYSTEM, L.P.;REEL/FRAME:022867/0485
Effective date: 20090420
|Oct 28, 2014||FPAY||Fee payment|
Year of fee payment: 4